CN101855270B - Polycarbonate diol - Google Patents
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- CN101855270B CN101855270B CN200880116028.4A CN200880116028A CN101855270B CN 101855270 B CN101855270 B CN 101855270B CN 200880116028 A CN200880116028 A CN 200880116028A CN 101855270 B CN101855270 B CN 101855270B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/44—Polycarbonates
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
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- C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
- C08G64/02—Aliphatic polycarbonates
- C08G64/0208—Aliphatic polycarbonates saturated
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- C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
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- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
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Abstract
A polycarbonate diol comprising repeating units represented by the following formula (A) and having terminal hydroxy groups, 60-100 mol% of the repeating units represented by the formula (A) being repeating units represented by the following formula (B) or (C). The amount of the repeating units represented by the formula (B) is 60-100 mol% based on the total amount of the repeating units represented by the formula (A). The polycarbonate diol has a terminal primary OH proportion of 95% or higher. (A) (In the formula, R represents a C2-12 divalent aliphatic or alicyclic hydrocarbon).
Description
Technical field
The present invention relates to be suitable as the polycarbonate diol of the raw material of urethane, thermoplastic elastomer etc., or, be suitable as the polycarbonate diol of the constituent material of coating, tackiness agent etc.In more detail, the present invention relates to access with using the situation of existing polycarbonate diol and compare, intensity, elongation, rebound resilience (resilience) is more excellent and the chemical proofing such as oil resistant is acid, resistance to chlorine also excellent urethane, the polycarbonate diol of thermoplastic elastomer.
Background technology
Known polycarbonate diol is, such as the soft chain segment as urethane, thermoplastic elastomer etc., and the starting material that hydrolytic resistance, photostabilization, resistance to oxidation deterioration, thermotolerance etc. are excellent.Yet, owing to having crystallinity with 1,6-hexylene glycol as the polycarbonate diol of raw material, therefore, use the urethane of this polycarbonate diol to there is flexibility, shortcoming that elastic restoration ratio is low.In order to address these problems, a kind of aliphatics Copolycarbonate glycol that uses two or more dibasic alcohol is disclosed.Wherein, the aliphatics Copolycarbonate glycol that particularly uses BDO is as accessing the polycarbonate diol of thermoplastic elastomer of the chemical proofing excellences such as oil resistant acidity, resistance to chlorine and receive publicity (with reference to patent documentation 1,2).
On the other hand, using polycarbonate diol as urethane, the raw material of thermoplastic elastomer, polyurethane elastomeric fiber etc., or while using as the constituent material of coating, tackiness agent etc., itself and isocyanic ester etc. have with the compound of the functional group of hydroxyl reaction and react and be used.Here, have with the compound of functional group of hydroxyl reaction and the reactivity of polycarbonate diol for produce and the quality of product all extremely important.Especially when the speed of polymerization is slow, can not bring up to target molecular weight.In addition the urethane obtaining,, the intensity of thermoplastic elastomer, elongation, rebound resilience can reduce.
So far, in order to control the speed of response of above-mentioned reaction, various polycarbonate diols and manufacture method thereof are disclosed.Aliphatics Copolycarbonate glycol as using BDO, discloses the polycarbonate diol (with reference to patent documentation 3) that does not use reaction control agent just to have stable polyurethane reactive.On the other hand, in the compound of functional group and the reactivity of polycarbonate diol that have with hydroxyl reaction, the polymer ends hydroxyl of polycarbonate diol is also very important.About the polymer ends hydroxyl of polycarbonate diol, disclosing with dialkyl carbonate or diaryl carbonate and polyol is the method (with reference to patent documentation 4,5) that end that raw material is manufactured polycarbonate diol is entirely the polycarbonate diol of hydroxyl substantially.The object of these methods is, solution is when manufacturing polycarbonate diol with dialkyl carbonate or diaryl carbonate as carbonic ether raw material, in the remaining alkyl of carbonic ether, the problem of aryl of being derived from of polymer ends, manufacturing polymer ends is substantially all the polycarbonate diol of hydroxyl.In these patent documentations, not about the kind of hydroxyl of polymer ends, the record of its control.
In addition, the polycarbonate diol (with reference to patent documentation 6) with high terminal primary hydroxyl ratio is disclosed.This polycarbonate diol can access high polymerization velocity, but the composition of its repeating unit of recording is far from being fully on chemical proofing.In addition, disclose and made the polycarbonate diol (with reference to patent documentation 7) that the ratio of polymer ends hydroxyl is particular value.Yet according to the ratio of disclosed polymer ends hydroxyl, the urethane of high molecular can not polymerization, and then it has only stipulated the ratio of polymer ends hydroxyl, but not about the record of primary hydroxyl shared in this hydroxyl.
As mentioned above, in the prior art, can access intensity, elongation, rebound resilience excellent, so the chemical proofing such as oil resistant acidity, resistance to chlorine also the urethane, the polycarbonate diol of thermoplastic elastomer of excellence are non-existent.
Patent documentation 1: No. 2885872 specification sheets of Japanese Patent
Patent documentation 2: TOHKEMY 2007-2248 communique
Patent documentation 3: No. 3128275 specification sheets of Japanese Patent
Patent documentation 4: No. 2570300 specification sheets of Japanese Patent
Patent documentation 5: No. 3724561 specification sheets of Japanese Patent
Patent documentation 6: No. 3874664 specification sheets of Japanese Patent
Patent documentation 7: TOHKEMY 2006-104253 communique
Summary of the invention
the problem that invention will solve
The present invention relates to be suitable as the polycarbonate diol of the raw material of urethane, thermoplastic elastomer etc., or, be suitable as the polycarbonate diol of the constituent material of coating, tackiness agent etc.In more detail, the object of the invention is to, provide can access with using the situation of existing polycarbonate diol and compare, the chemical proofings such as intensity, elongation, rebound resilience excellence and oil resistant acidity, resistance to chlorine are excellent urethane, the polycarbonate diol of thermoplastic elastomer also.
for the scheme of dealing with problems
In order to address the above problem, the inventor conducts in-depth research, found that, in the polycarbonate diol that comprises the repeating unit shown in following formula (A) and terminal hydroxyl, summation with respect to the repeating unit shown in formula (A), making amount and the terminal primary hydroxyl ratio of the repeating unit shown in following formula (B) is specific scope, can access thus with using the situation of existing polycarbonate diol and compare, intensity, elongation, rebound resilience excellence and oil resistant are acid, the chemical proofings such as resistance to chlorine are the urethane of excellence also, thermoplastic elastomer, thereby completed the present invention.
That is, the invention relates to the invention of following (1)～(5).
(1) a kind of polycarbonate diol, wherein, this polycarbonate diol comprises repeating unit and the terminal hydroxyl shown in following formula (A), 60～100 % by mole of repeating unit shown in this formula (A) be following formula (B) or (C) shown in repeating unit, and the amount of the repeating unit shown in formula (B) is that 60～100 % by mole, terminal primary hydroxyl ratio are more than 95% with respect to the summation of the repeating unit shown in formula (A).
[Chemical formula 1]
(wherein, the R in formula represents divalence aliphatics or the clicyclic hydrocarbon of carbonatoms 2～12.)
[Chemical formula 2]
[chemical formula 3]
(2) according to the polycarbonate diol (1) described, wherein, 65～100 % by mole of repeating unit shown in aforementioned formula (A) be above-mentioned formula (B) or (C) shown in repeating unit, and the amount of the repeating unit shown in formula (B) is 60～95 % by mole with respect to the summation of the repeating unit shown in formula (A).
(3) according to the polycarbonate diol (1) or (2) described, wherein, aforementioned terminal primary hydroxyl ratio and end secondary hydroxyl ratio sum are more than 98.5%.
(4) according to the polycarbonate diol described in any one of (1)～(3), wherein, 90～100 % by mole of repeating unit shown in aforementioned formula (A) be aforementioned formula (B) or (C) shown in repeating unit, the amount of the repeating unit shown in formula (B) is 70～95 % by mole with respect to the summation of the repeating unit shown in formula (A), and number-average molecular weight is 300～20000.
(5) thermoplastic polyurethane, it carries out copolymerization by the polycarbonate diol to described in any one of polyisocyanates and (1)～(4) and obtains.
invention effect
The invention provides the polycarbonate diol most suitable as the raw material of urethane, thermoplastic elastomer etc., or, most suitable as the polycarbonate diol of the constituent material of coating, tackiness agent etc.In more detail, the present invention has following effect: also excellent urethane, the polycarbonate diol of thermoplastic elastomer such as the chemical proofing that can obtain intensity, elongation, rebound resilience excellence and oil resistant acidity, resistance to chlorine can be provided.
Embodiment
Below, the present invention is described particularly.
Using polycarbonate diol as urethane, the raw material of thermoplastic elastomer, polyurethane elastomeric fiber etc., or, while using as the constituent material of coating, tackiness agent etc., itself and isocyanic ester are such has with the compound of the functional group of hydroxyl reaction and reacts and be used.The reactivity of these compounds and polycarbonate diol is extremely important.When particularly the speed of polymerization is slow, can occur to bring up to target molecular weight and, the problem that reduces of the urethane, the intensity of thermoplastic elastomer, elongation, the rebound resilience that obtain.The present invention has found out the optimum value of terminal primary hydroxyl ratio in polycarbonate diol, can access urethane, thermoplastic elastomer that the problems referred to above do not occur substantially.
In the present invention, terminal primary hydroxyl ratio refers to, by stirring under the pressure below 0.4kPa by polycarbonate diol (70g～100g) and heating at the temperature of 160 ℃～200 ℃, obtain being equivalent to the cut of amount of approximately 1～2 % by weight of this polycarbonate diol, the i.e. cut of about 1g (0.7～2g), use about 100g (95～105g) ethanol to be reclaimed as solvent, the gas-chromatography for solution (GC) that recovery obtains is analyzed, the value of the peak area by the chromatogram that obtains, the value calculating according to following formula (1).
Terminal primary hydroxyl ratio (%)=B ÷ A * 100 (1)
A: the summation of the peak area of the alcohols that comprises dibasic alcohol (except ethanol)
B: the summation of the peak area of the dibasic alcohol that two ends are primary hydroxyl
Terminal primary hydroxyl ratio refers to the shared ratio of primary hydroxyl in whole terminal group of polycarbonate diol.That is, as mentioned above, under the pressure by polycarbonate diol below 0.4kPa, while being heated to the temperature of 160 ℃～200 ℃, the terminal portions of polycarbonate diol is evaporated as alcohols, obtains (with reference to following formula (a)) as cut.
[chemical formula 4]
(in formula, R represents hydrocarbon.)
The ratio of the dibasic alcohol that in all alcohols in this cut, two ends are primary hydroxyl is terminal primary hydroxyl ratio.
Terminal primary hydroxyl ratio is 95% when above, can access intensity, elongation, the urethane of rebound resilience excellence, thermoplastic elastomer.Terminal primary hydroxyl ratio is lower than 95% time, and molecular weight can not be brought up to target value or need long situation more, and productivity reduces, but also has the tensile strength of resulting urethane, thermoplastic elastomer, the problem that rebound resilience reduces.Terminal primary hydroxyl ratio is 97% when above, and the problems referred to above are difficult for occurring, and then regardless of the reactivity of the isocyanic ester using, reaction can stabilization, therefore preferably.Terminal primary hydroxyl ratio is 98% when above, and the problems referred to above do not occur substantially, for more preferably.
In polycarbonate diol, the composition of repeating unit has a great impact the flexibility of the urethane that uses this polycarbonate diol to obtain, thermoplastic elastomer, chemical proofing.About polycarbonate diol of the present invention, the following formula (B) in the repeating unit shown in following formula (A) or (C) shown in repeating unit ratio (following, be called C46 ratio.) be 60～100 % by mole.C46 ratio is during lower than 60 % by mole, has chemical proofing deficiency, the impaired situation of flexibility occurs, therefore not preferred.When C46 ratio is 65～100%, can access urethane, the thermoplastic elastomer of the balance excellence of chemical proofing and flexibility, therefore preferably.When C46 ratio is 90～100 % by mole, the balance of chemical proofing and flexibility is best, therefore more preferably.
In polycarbonate diol of the present invention, with respect to the summation of the repeating unit shown in following formula (A), the ratio of following formula (B) (following, be called C4 ratio.) be 60～100 % by mole.C4 ratio during lower than 60 % by mole, according to the kind of pharmaceutical chemicals, has the situation that can not obtain sufficient chemical proofing, therefore not preferred.When C4 ratio approaches 100%, the urethane obtaining, the chemical proofing of thermoplastic elastomer increase, but the crystallinity of polycarbonate diol becomes extremely strong, according to the composition of urethane, thermoplastic elastomer, and the situation that has flexibility to reduce.When C4 ratio is 60～95%, can accesses high chemical proofing and can not damage flexibility, therefore preferably.When C4 ratio is 70～95 % by mole, can access high flexibility and chemical proofing, therefore most preferably.
[chemical formula 5]
(wherein, the R in formula represents divalence aliphatics or the clicyclic hydrocarbon of carbonatoms 2～12.)
[chemical formula 6]
[chemical formula 7]
There is no particular limitation for the manufacture method of polycarbonate diol of the present invention.For example, can show by Schnell, Polymer Reviews the 9th volume, the whole bag of tricks of recording in p9～20 (1994) is manufactured.
Polycarbonate diol of the present invention can be used BDO and 1,6-hexylene glycol to manufacture as dibasic alcohol.And then, also can add and be selected from ethylene glycol, 1,3-PD, 1,5-PD, 1,7-heptanediol, 1,8-ethohexadiol, 1,9-nonanediol, decamethylene-glycol, 1,11-undecane glycol, 1,12-dodecanediol etc. does not have the dibasic alcohol of side chain; 2-methyl isophthalic acid, 8-ethohexadiol, 2-ethyl-1,6-hexylene glycol, 2-methyl isophthalic acid, ammediol, 3-methyl isophthalic acid, 5-pentanediol, 2,4-dimethyl-1,5-PD, 2,4-diethyl-1,5-pentanediol, 2-butyl-2-ethyl-1, ammediol, 2，2-dimethyl-1，3-propanediol etc. are with the dibasic alcohol of side chain; One kind or two or more dibasic alcohol in 1,4 cyclohexane dimethanol, two (4-the hydroxy-cyclohexyl)-cyclic diols such as propane of 2-is as raw material.As long as addition can meet condition of the present invention, there is no particular limitation.In addition, also can use the compound in 1 a small amount of molecule with 3 above hydroxyls, for example, trimethylolethane, TriMethylolPropane(TMP), hexanetriol, tetramethylolmethane etc.The compound in this 1 molecule with 3 above hydroxyls is used when too much, thereby it crosslinked in the polyreaction of polycarbonate gelation occurs.Therefore,, with respect to the total amount of BDO and 1,6-hexylene glycol, the compound in 1 molecule with 3 above hydroxyls is that 0.01～5 % by weight is preferred.0.01～1 % by weight more preferably.
About polycarbonate diol of the present invention, as carbonic ether, can list the dialkyl carbonates such as methylcarbonate, diethyl carbonate, dipropyl carbonate, dibutyl carbonate; The diaryl carbonates such as diphenyl carbonate; Ethylene carbonate, carbonic acid Sanya methyl esters (Trimethylene Carbonate), carbonic acid 1, the sub-propyl ester (1 of 2-, 2-PropyleneCarbonate), carbonic acid 1,2-Aden ester (1,2-Buthylene Carbonate), carbonic acid 1 ，3-Aden ester (1,3-Buthylene Carbonate), carbonic acid 1, the alkylene carbonates such as the sub-pentyl ester of 2-(1,2-pentylene Carbonate).Can use one kind or two or more carbonic ether in them as raw material.From the easy degree that obtains, the viewpoint of the easy degree of the setting of the condition of polyreaction consider, preferably use methylcarbonate, diethyl carbonate, diphenyl carbonate, dibutyl carbonate, ethylene carbonate.
The manufacture of polycarbonate diol of the present invention can be added catalyzer, also can not add catalyzer.While adding catalyzer, can from common catalyst for ester exchange reaction, freely select.For example, can use metal or its salt, alkoxide (alkoxide) or the organic compound such as lithium, sodium, potassium, rubidium, caesium, magnesium, calcium, strontium, barium, zinc, aluminium, titanium, cobalt, germanium, tin, lead, antimony, arsenic, cerium.Particularly preferably be the compound of titanium, tin, lead.In addition, the consumption of catalyzer is generally 0.00001～0.1% of polycarbonate diol weight.
As an example of manufacture method, narrated and used methylcarbonate as the method for carbonic ether.The manufacture of polycarbonate diol divides 2 steps to carry out.Dibasic alcohol and methylcarbonate be take to the ratio that mol ratio is 20: 1 to 1: 10 mixed, under normal pressure or decompression, 100～300 ℃ of reactions, the methyl alcohol of generation, as removing with the mixture of methylcarbonate, obtains low-molecular polycarbonate glycol.Then, under reduced pressure, 160～250 ℃ of heating, remove unreacted dibasic alcohol and methylcarbonate, and make low-molecular polycarbonate glycol from condensation, obtain the polycarbonate diol of regulation molecular weight.
The polycarbonate diol with terminal primary hydroxyl ratio of the present invention is the polymerizing conditions such as purity from raw material dibasic alcohol, temperature, time, and in the conditions such as input ratio of the dibasic alcohol when using dialkyl carbonate and/or diaryl carbonate as carbonic ether and carbonic ether, select 1 appropriately combined these condition of conditioned disjunction to obtain.Industrial obtain 1, Isosorbide-5-Nitrae-cyclohexanediol that 6-hexylene glycol comprises 0.1～2 % by weight etc. has the impurity of secondary hydroxyl.The transesterification reaction of the dibasic alcohol with secondary hydroxyl when manufacturing polycarbonate diol is low, and therefore, its situation of terminal group that becomes polycarbonate diol is more, and result, forms the polycarbonate diol that end has secondary hydroxyl.When using dialkyl carbonate and/or diaryl carbonate as carbonic ether, the molecular weight of corresponding target polycarbonate diol, dibasic alcohol and carbonic ether are dropped into react with stoichiometric quantity or the ratio that approaches stoichiometric quantity, and the alkyl, the aryl that are derived from carbonic ether are more in the remaining situation of the end of polycarbonate diol.Therefore, by making that amount with respect to the dibasic alcohol of carbonic ether is stoichiometric quantity 1.01～1.30 times, can make to reduce at the remaining alkyl of the end of polycarbonate diol, aryl end.In addition, due to side reaction, the end of polycarbonate diol becomes vinyl, for example, while using methylcarbonate as carbonic ether, becomes methyl esters, methyl ether.Conventionally, temperature of reaction is higher, the reaction times is longer, and side reaction more easily occurs.
Terminal primary hydroxyl ratio is preferably adjusted to and makes the end of polycarbonate diol is secondary hydroxyl.When the end of polycarbonate diol is the alkyl that is derived from carbonic ether, aryl, or while being vinyl, in the polyreaction of urethane, thermoplastic elastomer, it has the function of chain terminator, according to the difference of target molecular weight, be sometimes difficult to bring up to target molecular weight.In addition, the molecular weight distribution that has resulting urethane, thermoplastic elastomer broadens, intensity, the impaired situation of rebound resilience.
End secondary hydroxyl ratio of the present invention refers to, adopts the method identical with terminal primary hydroxyl ratio to analyze, by the value of the peak area of resulting chromatogram, the value calculating according to following formula (2).
End secondary hydroxyl ratio (%)=C ÷ A * 100 (2)
A: the summation of the peak area of the alcohols that comprises dibasic alcohol (except ethanol)
C: the summation of peak area with the dibasic alcohol of at least 1 secondary hydroxyl
When polymer ends is secondary hydroxyl, the dibasic alcohol that hydroxyl at least is on one side secondary hydroxyl is left away (with reference to following formula (b)) from polymer ends.
[chemical formula 8]
(in formula, R, R
1, R
2represent hydrocarbon.)
In all alcohols in this cut, the ratio of the dibasic alcohol that at least 1 hydroxyl is secondary hydroxyl is end secondary hydroxyl ratio.
The terminal primary hydroxyl ratio of polycarbonate diol of the present invention and end secondary hydroxyl ratio and be more than 98.5% to be preferred.If terminal primary hydroxyl ratio and end secondary hydroxyl ratio and be more than 98.5%, the molecular weight of urethane, thermoplastic elastomer becomes target value, therefore preferably.In addition, molecular weight distribution can not occur and broaden, the intensity of urethane, thermoplastic elastomer, rebound resilience reduce, therefore preferably.Terminal primary hydroxyl ratio and end secondary hydroxyl ratio and be 99.0% when above, can access urethane, the thermoplastic elastomer of target molecular weight, and not be subject to used isocyanic ester, the impact of reaction conditions, therefore more preferably; Be 99.5% when above, can access intensity, the urethane of rebound resilience excellence, thermoplastic elastomer, therefore most preferably.
In order to adjust terminal primary hydroxyl ratio and/or end secondary hydroxyl ratio, can optionally add the dibasic alcohol with secondary hydroxyl.The dibasic alcohol with secondary hydroxyl can add in raw material, can in the process of manufacturing polycarbonate diol, add, and also can after becoming the molecular weight of regulation, add.For the method for adding the dibasic alcohol with secondary hydroxyl and carry out heat treated in the polycarbonate diol obtaining, its heat treated temperature is 120 ℃～190 ℃, is preferably 130 ℃～180 ℃.Heating temperature is during lower than 120 ℃, and reaction is slow, the cost treatment time, there is problem economically, and while surpassing 190 ℃, the possibility that produces the problem such as painted uprises.The heat treated time is according to temperature of reaction, treatment process and difference, but be generally 15 minutes～10 hours.As the dibasic alcohol with secondary hydroxyl, can list 1,2-PD, 1,3 butylene glycol, 1,2-pentanediol, Isosorbide-5-Nitrae-pentanediol, 1,2-hexylene glycol, 1,5-hexylene glycol, 2-ethyl-1,3-hexylene glycol, 1,2-ethohexadiol, 1,2-decanediol etc. has the dibasic alcohol of primary hydroxyl and secondary hydroxyl; 1,2-encircles pentanediol, 1, and 3-encircles pentanediol, 1,3-cyclohexanediol, Isosorbide-5-Nitrae-cyclohexanediol, 2,3-butanediol, 2, and 4-pentanediol, 2,5-hexylene glycol, 3,5-heptanediol etc. has the dibasic alcohol of 2 secondary hydroxyls; 2-methyl-2,4-pentanediol etc. has the dibasic alcohol of 1 secondary hydroxyl and 1 tert-hydroxyl.These dibasic alcohol can be used separately or mix two or more use.
The molecular weight preferred number average molecular weight of polycarbonate diol of the present invention is 300～20000.Number-average molecular weight is 300 when above, and flexibility, the cold property of the thermoplastic polyurethane obtaining are abundant, is 20000 when following, and the forming process of the thermoplastic polyurethane obtaining can not reduce, therefore preferably.More preferably the scope that number-average molecular weight is 450～5000.More preferably 500～3000.
Number-average molecular weight of the present invention obtains as follows: by using acetic anhydride and pyridine, " neutralization titration (the JIS K0070-1992) " that with the ethanolic soln of potassium hydroxide, carry out titration decides hydroxyl value and calculate by following formula (3).
(hydroxyl value * 10, number-average molecular weight=2/
-3/ 56.1) (3)
Polycarbonate diol of the present invention is to use 1,4-butyleneglycol and 1,6-hexylene glycol is as the polycarbonate diol of dibasic alcohol, by making the composition of its repeating unit and terminal primary hydroxyl ratio in specific scope, resulting urethane, thermoplastic elastomer, except the urethane that possesses existing use polycarbonate diol and obtain, hydrolytic resistance that thermoplastic elastomer has, thermotolerance, also have the characteristic of the chemical proofings such as oil resistant acidity, resistance to chlorine and intensity, flexibility, elastic restoring force excellence concurrently.Can access the raw material that is suitable as urethane, thermoplastic elastomer etc., or, be suitable as the polycarbonate diol of the constituent material of coating, tackiness agent etc.
By polycarbonate diol of the present invention is reacted with polyisocyanates, can access thermoplastic polyurethane.
The polyisocyanates using as manufacture thermoplastic polyurethane of the present invention, for example has 2,4 toluene diisocyanate, 2,6-tolylene diisocyanate and composition thereof (TDI); Ditane-4,4 '-vulcabond (MDI), naphthalene-1,5-vulcabond (NDI), 3,3 '-dimethyl-4, the known aromatic diisocyanates such as 4 '-biphenyl diisocyanate, rough TDI, polymethylene polyphenyl isocyanate, rough MDI; The known fragrant alicyclic diisocyanates such as xylylene vulcabond (XDI), phenylene vulcabond; 4, the known aliphatic diisocyanates such as 4 '-methylene-bis-cyclohexyl diisocyanate (hydrogenation MDI), hexamethylene diisocyanate (HMDI), isophorone diisocyanate (IPDI), cyclohexyl diisocyanate (hydrogenation XDI); And isocyanuric acid esterification modification product of these isocyanates, carbodiimide modification product, biuretized modification product etc.
In the manufacture of thermoplastic polyurethane of the present invention, as copolymer composition, can use chain extension agent.As chain extension agent, can use the conventional chain extension agent of urethane industry.As the example of chain extension agent, can list the water, low molecular polylol, polyamines of 25th～27 pages of known chain extension agents of conduct of recording of the up-to-date urethane utilisation technology of the < < > > that rock Tian Jing controls chief editor (by Japanese CMC Cinema Magnetique Communication distribution in 1985) etc.In addition,, according to the purposes of thermoplastic polyurethane, in the scope of not damaging effect of the present invention, can be used in combination the known macromolecule polyol as chain extension agent.Example as known macromolecule polyol, can list the good husband's work of modern well < < polyurethane foam > > (Japanese polymer distribution meeting, 1987) 12nd～23 pages of known polyester polyols of recording, there is the macromolecule polyols such as polyether carbonate (that is, polyether carbonate polyol) of polyoxyalkylene chain (polyoxyalkylene chain).Specifically, as the above-mentioned low molecular polylol as chain extension agent, conventionally using molecular weight is the dibasic alcohol below 300.As low molecular polylol, for example, can list ethylene glycol, 1,3-PD, BDO, 1,5-PD, 1, the aliphatic dihydroxy alcohols such as 6-hexylene glycol, neopentyl glycol, decamethylene-glycol.In addition, more examples as the low molecular polylol of chain extension agent, can list 1, ester ring type dibasic alcohol, the xylyl alcohols (xylylene glycol) such as 1-cyclohexanedimethanol, 1,4 cyclohexane dimethanol, tristane dimethanol, two (to hydroxyl) hexichol, two (p-hydroxybenzene) propane, 2, two [4-(2-hydroxy ethoxy) phenyl] propane of 2-, two [4-(2-hydroxyl) phenyl] sulfone, two [4-(2-hydroxy ethoxy) phenyl] hexanaphthenes of 1,1-etc.Preferably make spent glycol, BDO.
As the method for manufacturing thermoplastic polyurethane of the present invention, can use the technology of the known polyurethane-reinforcement reaction of urethane industry.For example, by make polycarbonate diol of the present invention and organic multiple isocyanate under atmospheric pressure, ℃ reaction in normal temperature～200, can manufacture thermoplastic polyurethane.While using chain extension agent, can reaction start add, also can in the process of reaction, add.For the manufacture method of thermoplastic polyurethane, for example can be with reference to No. 5070173rd, United States Patent (USP).
In polyurethane-reinforcement reaction, can use and take the known polymerizing catalyst that the organic metal salt etc. of tertiary amine, tin, titanium etc. is representative (for example, respect Jitian to control 23rd～32 pages of outstanding < < urethane resin > > (distribution of Japanese industry news agency, 1969) on the books).
In addition, polyurethane-reinforcement reaction also can be carried out with solvent, as the example of preferred solvent, can list dimethyl formamide, diethylformamide, N,N-DIMETHYLACETAMIDE, methyl-sulphoxide, tetrahydrofuran (THF), mibk, diox, pimelinketone, benzene, toluene, ethyl cellosolve etc.
In the manufacture of thermoplastic polyurethane of the present invention, can by only contain one with the compound of the active hydrogen of isocyanic ester radical reaction as monohydroxy-alcohols such as ethanol, propyl alcohol, and the secondary amine such as diethylamine, di-n-propylamine etc. is used as end terminator.
It is desirable to, in thermoplastic polyurethane of the present invention, add the stablizers such as thermo-stabilizer (such as antioxidant), photostabilizer.As antioxidant (thermo-stabilizer), can use the phosphorus compound such as aliphatic ester, aromatic ester or alkyl substituent aromatic ester, ortho phosphorous acid derivative, phenyl-phosphonic acid, phenyl phosphinic acid, diphenyl phosphonic acid, polyphosphonates, dialkyl group pentaerythritol diphosphate, dialkyl group dihydroxyphenyl propane bisphosphate of phosphoric acid, phosphorous acid; Phenol is derivative, especially hindered phenol compound; The sulfocompounds such as thioether system, dithionate system, mercaptobenzimidazole system, thiambutosine system, thiodipropionate; The tin based compounds such as toxilic acid tin (tin maleate), Dibutyltin oxide (DibutyltinMonoxide).Conventionally, antioxidant can be divided into once, secondary, three anti-aging agent.Especially as the hindered phenol of an anti-aging agent, preferred Irganox1010 (trade(brand)name; Switzerland CIBA-GEIGY company system), Irganox1520 (trade(brand)name; Switzerland CIBA-GEIGY company system) etc.As the phosphine based compound of secondary anti-aging agent, preferably PEP-36, PEP-24G, HP-10 (are trade(brand)name; Japan's rising sun electrification (strain) system), Irgafos168 (trade(brand)name; Switzerland CIBA-GEIGY company system).And then, as the sulphur compound of three anti-aging agent, the sulfide compounds such as preferred Tyox B (DLTP), distearyl thiodipropionate (DSTP).
As photostabilizer, can list ultraviolet radiation absorption type photostabilizer and free radical capture type photostabilizer.
As the example of ultraviolet radiation absorption type photostabilizer, can list benzotriazole system, benzophenone based compound etc.As the example of free radical capture type photostabilizer, can list hindered amine compound etc.These stablizers can be used singly or in combination of two or more thereof.
With respect to 100 weight part thermoplastic polyurethanes, the addition of these stablizers be 0.01～5 weight part be preferably, more preferably 0.1～3 weight part, 0.2～2 weight part more preferably.
In thermoplastic polyurethane of the present invention, also can add softening agent.As the example of softening agent, can list the phthalates such as dioctyl phthalate (DOP), dibutyl phthalate, diethyl phthalate, butyl benzyl phthalate, phthalic acid two (2-ethylhexyl) ester, phthalic acid diiso decyl ester, phthalic acid two (undecyl) ester, diisononyl phthalate; Tritolyl Phosphate, triethyl phosphate, tributyl phosphate, the phosphoric acid esters such as tri-2-ethylhexyl phosphate, the own ester of tricresyl phosphate methyl, tricresyl phosphate-chloroethene ester, tricresyl phosphate (two chloropropyls) ester; The fatty acid esters such as the trimellitate such as trioctyl trimellitate, triisodecyl trimellitate class, dipentaerythritol ester class, Octyl adipate, dimethyl adipate, nonane diacid two (2-ethylhexyl) ester, dioctyl azelate, dioctyl sebacate, sebacic acid two (2-ethylhexyl) ester, methyl acetyl ricinoleate; The pyromellitic esters such as pyromellitic acid monooctyl ester; The epoxies such as epoxidised soybean oil, epoxidised linseed oil, epoxidized fatty acid alkyl ester are softening agent; The polyethers such as hexanodioic acid ether-ether, polyethers are softening agent; The liquid rubbers such as liquid NBR, liquid methacrylate rubber, liquid polybutadiene; Non-aromatic through-stone wax oil etc.These softening agent can be used singly or in combination of two or more thereof.The addition of softening agent hardness, physical property as required suitably selected, and with respect to 100 weight part thermoplastic polyurethanes, is preferably 0.1～50 weight part.
And then, in thermoplastic polyurethane of the present invention, also can add inorganic filler, lubricant, tinting material, silicone oil, whipping agent, fire retardant etc.As inorganic filler, such as listing calcium carbonate, talcum, magnesium hydroxide, mica, barium sulfate, silicic acid (white carbon black), titanium oxide, carbon black etc.These various additives can be used normally used amount in existing thermoplastic polyurethane.
The Shore D hardness of thermoplastic polyurethane of the present invention is preferably 20～70, more preferably 25～50 scope.Shore D hardness is 20 when above, and thermotolerance, scoring resistance are enough high, and in addition, Shore D hardness is 70 when following, does not have the problem of resulting low-temperature performance, soft feel(ing) deficiency.
Molecular weight for thermoplastic polyurethane of the present invention, preferably, the number-average molecular weight that is converted into polystyrene (Mn) of measuring by gpc analysis and the weight-average molecular weight that is converted into polystyrene (Mw) of measuring by gpc analysis are respectively 10000～200000 scope.
Embodiment
Below, by embodiment and comparative example, illustrate in greater detail the present invention.
1. the decision of terminal primary hydroxyl ratio
Take the polycarbonate diol of 70g～100g in the eggplant type bottle of 300ml, use is connected with the Rotary Evaporators that cut reclaims the recovery ball (trap ball) of use, under pressure below 0.4kPa, heating bath by approximately 180 ℃ heats and stirs, in reclaiming ball, obtain being equivalent to the cut of approximately 1～2 % by weight of this polycarbonate diol, i.e. the cut of about 1g (0.7～2g).With the ethanol of about 100g (95～105g), as this cut of solvent recuperation, the solution of recovery is carried out to gas chromatographic analysis, and (below, being called GC analyzes.), by the value of the peak area of the chromatogram obtaining, by following formula (1), calculate terminal primary hydroxyl ratio.In addition, GC analyze to be used the gas-chromatography 6890 (U.S. Hewlett-Packard system) as post with the DB-WAX (U.S. J & W society system) of 30m, thickness 0.25 μ m, and detector uses flame ionization ditector (FID).The heating schedule of post is with 10 ℃/min, to be warmed up to 250 ℃ from 60 ℃, then at this temperature, keeps 15 minutes.The evaluation at each peak during GC analyzes is carried out with following GC-MS device.GC device is used with DB-WAX (U.S. J & W society system) 6890 (U.S. Hewlett-Packard systems) as post, from 40 ℃ of initial temperatures, with 10 ℃/min of heat-up rate, is warmed up to 220 ℃.MS device is used Auto-massSUN (Japanese JEOL system), at ionization voltage, is that 70eV, sweep limit m/z=10～500, multiplier gain are to carry out under 450V.
Terminal primary hydroxyl ratio (%)=B ÷ A * 100 (1)
A: the summation of the peak area of the alcohols that comprises dibasic alcohol (except ethanol)
B: the summation of the peak area of the dibasic alcohol that two ends are primary hydroxyl
2. the decision of end secondary hydroxyl ratio
Adopt the method identical with terminal primary hydroxyl ratio to carry out GC analysis, by the value of the peak area of the spectrogram obtaining, by following formula (2), calculate end secondary hydroxyl ratio.
End secondary hydroxyl ratio (%)=C ÷ A * 100 (2)
A: the summation of the peak area of the alcohols that comprises dibasic alcohol (except ethanol)
C: the summation of peak area with the dibasic alcohol of at least 1 secondary hydroxyl
The decision of 3.C4 ratio and C46 ratio
Take 1g sample in the eggplant type bottle of 100ml, add 30g ethanol, 4g potassium hydroxide, in the oil bath of 100 ℃, heat 1 hour.After cool to room temperature, add 1～2 phenolphthalein indicator, with hydrochloric acid, neutralize.In refrigerator and cooled, but after 3 hours, the salt of sedimentation, by removing by filter, is carried out to GC analysis.C4 ratio is calculated respectively by following formula (5) by following formula (4), C46 ratio.In addition, GC analyze to be used with the DB-WAX (U.S. J & W society system) of 30m, thickness 0.25 μ md as the gas-chromatography GC14B (Shimadzu Seisakusho Ltd.'s system) of post, uses Diethylene Glycol diethyl ester as interior mark, and detector uses flame ionization ditector (FID) to carry out.The heating schedule of post is after 5 minutes, with 10 ℃/min, to be warmed up to 250 ℃ 60 ℃ of maintenances.
C4 ratio (% by mole)=D ÷ F * 100 (4)
C46 ratio (% by mole)=(D+E) ÷ F * 100 (5)
D:GC analyzes the mole number of the BDO obtaining
E:GC analyze obtain 1, the mole number of 6-hexylene glycol
F:GC analyzes the summation of the mole number of the dibasic alcohol obtaining
4. the purity check of raw material dibasic alcohol
The BDO using as dibasic alcohol raw material and 1,6-hexylene glycol are by gas chromatographic analysis.Condition is: use with DB-WAX (J & W system) as the gas-chromatography GC-14B (Shimadzu Seisakusho Ltd.'s system) of post, using Diethylene Glycol diethyl ester as interior mark, the FID of usining carries out as detector.In addition, the heating schedule of post is to keep, after 5 minutes, with 10 ℃/min, being warmed up to 250 ℃ at 60 ℃.
The purity of BDO is that 99.6%, 0.4 % by weight is multiple not clear peak.The purity of 1,6-hexylene glycol is 99.0 % by weight, the Isosorbide-5-Nitrae-cyclohexanediol that comprises 0.7 % by weight.Remaining 0.3 % by weight is multiple not clear thing.
5. the molecular weight of thermoplastic polyurethane and evaluation of physical property
(1) number-average molecular weight and weight-average molecular weight, the calibration curve negotiating GPC that uses polystyrene standard to obtain measures.
(2) Shore D hardness (without unit)
ASTM D2240, D type is measured at 23 ℃.
(3) tensile strength (kgf/cm
2)
JIS K6251, No. 3 dumbbells, test films are used the thick compressing tablet (presssheet) of 2mm.
(4) elongation (%)
JIS K6251, No. 3 dumbbells, test film is used the thick compressing tablet of 2mm.
(5) rebound resilience (%)
JIS K6255, Lupke put (Lupke pendulum)
(6) chemical proofing
The polyurethane film that formation thickness is 0.07～0.10mm floods this film 1 week in the oleic acid (1 grade of reagent) of 45 ℃, measures swelling capacity, as the index of chemical proofing.Swelling ratio calculates by following formula (6).
Weight * 100 (6) before swelling ratio (%)=(weight before the weight-test after test)/test
(embodiment 1)
In possessing the glass flask processed that is filled with the rectifying tower of regular weighting material and the 1L of whipping appts, add 280g (3.1mol) methylcarbonate, 200g (2.2mol) BDO, 120g (1.0mol) 1,6-hexylene glycol.Add 0.10g tetrabutyl titanate as catalyzer, under normal pressure, stir and heat.Temperature of reaction slowly rises to 180 ℃ from 150 ℃, and heats up in a steamer the methyl alcohol that generates and the mixture of methylcarbonate, reacts 10 hours.Afterwards, decompression, to 17kPa, is heated up in a steamer the mixture of methyl alcohol and methylcarbonate, and further reacts 7 hours at 180 ℃.The analytical results of the polycarbonate diol obtaining is summarized in table 1.
(comparative example 1)
Except the add-on of raw material is 220g (1.9mol) methylcarbonate, 160g (1.8mol) BDO, 320g (3.6mol) 1, beyond 6-hexylene glycol, according to the method shown in embodiment 1, react.The analytical results of the polycarbonate diol obtaining is summarized in table 1.
(comparative example 2)
Except the add-on of methylcarbonate is 330g (3.7mol), adds in raw material 4.0g (0.03mol) Isosorbide-5-Nitrae-cyclohexanediol, according to the method shown in embodiment 1, react.The analytical results of the polycarbonate diol obtaining is summarized in table 1.
(embodiment 2)
Use the device shown in embodiment 1 to carry out polymerization.Add 420g (3.6mol) diethyl carbonate, 200g (2.2mol) BDO, 120g (1.0mol) 1,6-hexylene glycol.Add 0.09g tetrabutyl titanate as catalyzer, under normal pressure, stir and heat.Temperature of reaction is slowly elevated to 180 ℃ from 150 ℃, and heats up in a steamer the ethanol that generates and the mixture of diethyl carbonate, reacts 10 hours.Afterwards, decompression, to 18kPa, is heated up in a steamer the mixture of ethanol and diethyl carbonate, and further reacts 7 hours at 180 ℃.The analytical results of the polycarbonate diol obtaining is summarized in table 1.
(embodiment 3)
Use the device shown in embodiment 1 to carry out polymerization.Add 320g (3.6mol) ethylene carbonate, 250g (2.8mol) BDO, 100g (0.9mol) 1,6-hexylene glycol.Add 0.12g tetrabutyl titanate as catalyzer, under normal pressure, stir and heat.Temperature of reaction is slowly heated to 180 ℃ from 150 ℃, heats up in a steamer the ethylene glycol that generates and the mixture of ethylene carbonate, reacts 10 hours.Afterwards, decompression, to 15kPa, is heated up in a steamer dibasic alcohol and ethylene carbonate, at 180 ℃, further reacts 7 hours.The analytical results of the polycarbonate diol obtaining is summarized in table 1.
(embodiment 4)
Except add 5g (0.04mol) Isosorbide-5-Nitrae-cyclohexanediol in raw material, under the condition shown in embodiment 3, react.The analytical results of the polycarbonate diol obtaining is summarized in table 1.
(embodiment 5)
Except add 12g (0.1mol) Isosorbide-5-Nitrae-cyclohexanediol in raw material, under the condition shown in embodiment 3, react.The analytical results of the polycarbonate diol obtaining is summarized in table 1.
[table 1]
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Comparative example 1 | Comparative example 2 | |
| Number-average molecular weight | 2005 | 2010 | 1995 | 2005 | 1995 | 1995 | 2005 |
| Terminal primary hydroxyl ratio (%) | 98.5 | 96.6 | 99.5 | 98.4 | 96.4 | 98.1 | 94.8 |
| End secondary hydroxyl ratio (%) | 0.6 | 0.7 | 0.4 | 1.5 | 3.5 | 1.0 | 1.4 |
| C4 ratio (% by mole) | 64 | 63 | 73 | 72 | 73 | 42 | 62 |
| C46 ratio (% by mole) | 100 | 100 | 100 | 99 | 97 | 100 | 99 |
| The abbreviation of polycarbonate diol | PC-1 | PC-2 | PC-3 | PC-4 | PC-5 | PC-6 | PC-7 |
(embodiment 6)
The polycarbonate diol that 200g embodiment 1 is obtained (PC-1), 64.2g hexamethylene diisocyanate join in the reactor with whipping appts, thermometer, prolong, react 4 hours at 100 ℃, obtain the prepolymer of end NCO.In this prepolymer, add 27.0g 1,4-butyleneglycol reacts after 60 minutes as catalyzer, the built-in omnipotent forcing machine for LAB O (the made omnipotent forcing machine KR-35 type for LABO of Japan's (strain) large bamboo hat with a conical crown and broad brim pine chemical research) of use kneader as chain extension agent, 0.01g dibutyl tin laurate at 140 ℃, becomes particle in forcing machine.The number-average molecular weight that is scaled polystyrene obtaining by GPC of the thermoplastic polyurethane obtaining and weight-average molecular weight are shown in table 2 with the evaluation result of transitivity.
(embodiment 7～10)
Except using PC-2～5 as polycarbonate diol, according to the method described in embodiment 6, obtain thermoplastic polyurethane.The number-average molecular weight that is scaled polystyrene obtaining by GPC of the thermoplastic polyurethane obtaining and weight-average molecular weight are shown in table 2 with the evaluation result of transitivity.
(comparative example 3～4)
Except using PC-6～7 as polycarbonate diol, according to the method shown in embodiment 6, obtain thermoplastic polyurethane.The number-average molecular weight that is scaled polystyrene that the thermoplastic polyurethane obtaining obtains by GPC and weight-average molecular weight are shown in table 2 with the evaluation result of transitivity.
[table 2]
| Embodiment 6 | Embodiment 7 | Embodiment 8 | Embodiment 9 | Embodiment 10 | Comparative example 3 | Comparative example 4 | |
| Polycarbonate diol | PC-1 | PC-2 | PC-3 | PC-4 | PC-5 | PC-6 | PC-7 |
| Number-average molecular weight (10 4Mn) | 6.8 | 6.0 | 7.1 | 7.0 | 6.6 | 6.7 | 5.2 |
| Weight-average molecular weight (10 4Mw) | 14.6 | 13.2 | 15.1 | 14.9 | 14.2 | 14.4 | 12.7 |
| Hardness (Shore D) | 48 | 46 | 46 | 47 | 45 | 47 | 43 |
| Tensile strength (MPa) | 31 | 28 | 33 | 32 | 30 | 31 | 19 |
| Elongation (%) | 700 | 680 | 720 | 710 | 670 | 700 | 540 |
| Rebound resilience (%) | 48 | 44 | 51 | 49 | 47 | 47 | 38 |
| Swelling ratio (%) | 3.7 | 3.8 | 3.1 | 3.2 | 3.4 | 8.4 | 4.0 |
utilizability in industry
The present invention is can be in the balance of the physical property such as hydrolytic resistance, thermotolerance, flexibility excellent and have in the raw material of urethane, thermoplastic elastomer etc. of the chemical proofings such as high oil resistant acidity, resistance to chlorine and utilize, or, can utilize as the constituent material of coating, tackiness agent etc.
Claims (4)
1. a polycarbonate diol, wherein, described polycarbonate diol comprises repeating unit and the terminal hydroxyl shown in following formula (A), 60～100 % by mole of repeating unit shown in described formula (A) be following formula (B) or (C) shown in repeating unit, and, the amount of the repeating unit shown in formula (B) is 60～100 % by mole with respect to the summation of the repeating unit shown in formula (A), terminal hydroxyl comprises primary hydroxyl and secondary hydroxyl, terminal primary hydroxyl ratio is more than 97% below 99.5%, terminal primary hydroxyl ratio and end secondary hydroxyl ratio sum are more than 98.5%
This terminal primary hydroxyl ratio and end secondary hydroxyl ratio refer to, by stirring under the pressure below 0.4kPa by this polycarbonate diol of 70～100g and heating at the temperature of 160 ℃～200 ℃, obtain being equivalent to the cut of amount of 1～2 % by weight of this polycarbonate diol, use 95～105g ethanol as solvent, this cut to be reclaimed, the solution gas chromatographic analysis that recovery obtains, the value of the peak area of the chromatogram that use obtains, terminal primary hydroxyl ratiometer is shown to the summation of peak area and the per-cent of the summation of the peak area of the alcohols that comprises dibasic alcohol that two ends are the dibasic alcohol of primary hydroxyl, end secondary hydroxyl ratiometer is shown the summation of peak area and the per-cent of the summation of the peak area of the alcohols that comprises dibasic alcohol of the dibasic alcohol with at least 1 secondary hydroxyl, wherein, the described alcohols that comprises dibasic alcohol does not comprise ethanol,
Chemical formula 1]
Wherein, the R in formula represents divalence aliphatics or the clicyclic hydrocarbon of carbonatoms 2～12,
[Chemical formula 2]
[chemical formula 3]
2. polycarbonate diol according to claim 1, wherein, 65～100 % by mole of repeating unit shown in described formula (A) be described formula (B) or (C) shown in repeating unit, and the amount of the repeating unit shown in formula (B) is 60～95 % by mole with respect to the summation of the repeating unit shown in formula (A).
3. polycarbonate diol according to claim 1, wherein, 90～100 % by mole of repeating unit shown in described formula (A) be described formula (B) or (C) shown in repeating unit, the amount of the repeating unit shown in formula (B) is 70～95 % by mole with respect to the summation of the repeating unit shown in formula (A), and number-average molecular weight is 300～20000.
4. a thermoplastic polyurethane, it carries out copolymerization by the polycarbonate diol to described in any one of polyisocyanates and claim 1～3 and obtains.
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| JP2007297408 | 2007-11-16 | ||
| JP2007-297408 | 2007-11-16 | ||
| PCT/JP2008/070026 WO2009063767A1 (en) | 2007-11-16 | 2008-11-04 | Polycarbonate diol |
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| EP (1) | EP2213696B1 (en) |
| JP (1) | JP5123950B2 (en) |
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Also Published As
| Publication number | Publication date |
|---|---|
| JPWO2009063767A1 (en) | 2011-03-31 |
| CN101855270A (en) | 2010-10-06 |
| US20100261852A1 (en) | 2010-10-14 |
| WO2009063767A1 (en) | 2009-05-22 |
| EP2213696A1 (en) | 2010-08-04 |
| EP2213696B1 (en) | 2016-10-19 |
| KR20100055521A (en) | 2010-05-26 |
| TWI443125B (en) | 2014-07-01 |
| US8686107B2 (en) | 2014-04-01 |
| JP5123950B2 (en) | 2013-01-23 |
| TW200936638A (en) | 2009-09-01 |
| KR101187118B1 (en) | 2012-09-28 |
| EP2213696A4 (en) | 2011-12-14 |
| ES2600181T3 (en) | 2017-02-07 |
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